Catalytic methods for peroxide mediated oxidation

该项目将涉及发展综合方法，以对医疗保健技术、物理科学和未来制造业等主题领域具有重要意义的机械洞察力为指导。我们最近报道了一种在潮湿和空气存在下进行烯烃二羟基化的无金属方法。化学。Soc. 2010, 132, 14409)。用一等量的过氧化丙二醇处理烯烃（CHCl3; 0.5 M; r.t； H2O 1等量），然后水解，得到相应的二醇，分离收率为82-96%，syn选择性高达50:1。这是一种有效的烯烃二羟基化方法，与传统的过渡金属催化工艺相比，具有明显的优势，具有很大的发展潜力。为了充分发挥这一议定书的潜力，必须制定一种催化程序。因此，我们希望开展一个具有以下主要目标的项目：*开发一种新的烯烃二羟基化催化循环。*建立取代烯烃的工艺范围。表征催化循环的动力学和机理。该项目的成功成果将提供一种简单、有效且与工业相关的催化氧化程序，该程序可以在室温下、有水分和空气的情况下进行。

The project will involve development of synthetic methodology guided by mechanistic insight of importance to the thematic areas of Healthcare Technologies, Physical Sciences and Manufacturing the Future.We have recently reported a metal-free method for the dihydroxylation of alkenes that proceeds in the presence of both moisture and air (J. Am. Chem. Soc. 2010, 132, 14409). Treatment of an alkene with one equivalent of a malonoyl peroxide (CHCl3; 0.5 M; r.t.; H2O 1 equiv), followed by hydrolysis, gives the corresponding diol in 82-96% isolated yield with syn selectivity (up to 50:1). This represents an effective method for the dihydroxylation of alkenes which has significant advantages over traditional transition-metal catalysed processes and has great potential for development. In order to realise the full potential of this protocol a catalytic procedure must be developed. We therefore wish to undertake a project with the following major goals and objectives:* Develop a novel catalytic cycle for the dihydroxylation of alkenes.* Establish the scope of the process for substituted alkenes.* Characterise the kinetics and mechanism of the catalytic cycle.Successful outcome of this project will deliver a simple, effective and industry relevant catalytic oxidation procedure that proceeds at room temperature in the presence of moisture and air.